JPS6213462A - Novel aminophenols and use thereof in oxidizing hair dye - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The subject of the present invention is new m-aminophenols and their water-soluble salts. This compound is particularly suitable to a high degree as a coupling substance in oxidative hair dyes.

Dyeing of hair is produced by oxidative coupling of one or more color developing components with each other or with one or more coupling components. So-called oxidized dyes work well because of their strong color and very good fastness properties. Primary aromatic amines with free or substituted hydroxy or amine groups in the para- or ortho position, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and tetra Use aminopyrimidine. Examples of so-called coupling components include m-phenylenediamine salt conductors, phenols, naphthols, resorcinol derivatives, and pyrazolones.

Good oxidative hair dye components must first of all satisfy the following prerequisites: They form the desired shade with sufficient strength in oxidative coupling with the respective developer- or coupling-component. Must. The shade must have sufficient stability against the action of heat, light and chemicals, for example against the reducing agents used in the cold perming of hair. Furthermore, it must have good dyeing power on human hair without strongly staining the scalp;
Moreover, it must be free from toxicological and dermatological viewpoints.

This requirement is currently not fully met by the coupling substances customary in oxidative hair dyes, in particular by the coupling substances which produce blue tints with known color developer substances, such as p-tolylenediamine.

The toxicological properties of many coupling substances, such as those of the aromatic amine type, are particularly problematic. Other coupling substances result in dyeings that do not have sufficient fastness properties.

4-Chlor-3 as a coupling substance in oxidative hair dyes
The use of -aminophenols is known from German Patent Application No. 2509152. The use of chloro-methyl-3-aminophenol with a chloro or methyl group in the 2-position as a coupling substance in oxidative hair dyes is known from German Patent Application No. 3016008. Finally, as a coupling substance for the aromatic p-diamine type color developer, 2-amino-4-
Hydroxy-5-chlordolol is known from German Patent Application No. 1,543,808. However, the hair dyes which can be produced using the known m-aminophenols as coupling substances are unsatisfactory in terms of their fastness properties.

The inventors have now determined that the 2-methyl-4-chloro-5-
Aminophenols have been found to be particularly suitable as coupling substances for producing light- and rub-fast oxidative hair dyes.

The above m-aminophenols are not known in the literature.

Therefore, the object of the present invention is a novel m-aminophenol having the general formula (1) H (in which R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 2 to 4 carbon atoms) and its It is a water-soluble salt.

The preparation of the new m-aminophenol is based on the 4-chloro-2-methyl-
It is carried out by catalytic hydrogenation starting from 5-nitrophenol and forming 4-chloro-2-methyl-5-aminophenol.

The radical R can be introduced in known manner for the preparation of the aminophenols according to the invention of the general formula I, in which R is an alkyl- or hydroxyalkyl radical. For example, an alkyl group can be introduced by alkylation, for example with an alkyl iodite of the formula R1. The 2-hydroxyethyl group can be introduced as follows. That is, first, a 2-chloro-propionyl group is introduced into the nitrogen by acylation with chloroformic acid-2-chloroester, and this is cyclized to form 1.
, 3-oxazolidin-2-one, and finally hydrolyzed to form an N-(2-hydroxyethyl)- group.

Especially because of its easy availability, 4-chloro-2-methyl-
5-aminophenol is preferred.

However, particularly light-fast hair dyeings can also be obtained using 4-chloro-2-methyl-5-(2-hydroxyethyl)-aminophenol.

According to the invention, m-aminophenol can be produced in free form and in the form of its water-soluble salts, such as hydrochloride,
Sulfates, phosphates, acetates.

Can be used as propionate, lactate, citrate.

Other objects of the present invention are general formulas! The novel m-aminophenol or its salt is used as a pulling substance in an oxidative hair dye together with a conventional color developing substance.

The novel coupling substances according to the invention are compatible with many different color developing substances. This produces a deep blue, violet color on the hair depending on the color developer used.

Produces a red or brown tint. The m-aminophenol according to the present invention is converted to p-)unilenediamine.

Preferably, it is used with a color developer selected from the group consisting of I)-tolylenediamine, p-aminophenol or 2,4,5,6-tetraaminopyridine.

The coupling substances according to the invention have an increased stability in cream bases compared to 2-methyl-5-aminophenol, for example at elevated temperatures (in the incorporation process or in the production of dyeing creams). has unexpected advantages.

Another object of the invention is characterized in that it contains a coupling substance of the general formula I in an amount of 0.05-105-1 O per 100 g of hair dye and a customary color developer substance.

A hair dye containing an oxidized hair dye precursor in the form of a cosmetic carrier. The customary color developing substances are preferably p-fuynylene diamine, p-1 lylene diamine, p-aminophenol (and) or 2,4,5,6-titraaminopyridine in the hair dye according to the invention. Contains in.

In addition, the hair tones according to the invention may also be of other types.

Known color developer substances 1 may be included, such as the preferred color developer substances described above, diaminopyridine derivatives, heterocyclic hydrazones and 4-amino-pyrazolone derivatives, as well as other known coupling substances. Other suitable coupling substances include, for example, tbm-fuynylenediamine, phenols, naphthols, resorcinol derivatives 2, such as 2-methylresorcinol or pyrazolones.

Optionally direct dyes can additionally be used to further change the shade. Such blood staining dyes are, for example, nitrophenyl diamines, nitro-aminophenols, anthraquinone dyes or indophenols.

In the hair dye according to the invention, m-aminophenol of general formula I and optionally additionally present coupling substance are generally used in approximately equimolar amounts with respect to the color developer used. Although the use of equimolar amounts has proven advantageous, it is not disadvantageous to use an excess of the individual oxidation dye precursors. In this case, the color developing substance and the coupling substance may be contained in a molar ratio of 1:0.5 to 1:2.

In principle, oxidative color development for staining can be carried out using atmospheric oxygen. However, it is preferred to use chemical oxidizing agents. This is especially the case if, in addition to dyeing, a lightening effect is desired on the hair. Suitable oxidizing agents include, in particular, hydrogen peroxide or its addition products with urea, melamine or sodium borate, as well as mixtures of such hydrogen peroxide addition products with potassium peroxide disulfate.

To prepare the hair dye according to the invention, the oxidative dyestuff is incorporated in the form of a suitable cosmetic carrier.

Such carriers are, for example, creams, emulsions, gels or foamed solutions containing surfactants.

For example shampoos or other preparations suitable for use on hair. Common ingredients of such cosmetic preparations are, for example, humectants and emulsifiers.

For example, anionic, nonionic or amphoteric surfactants,
(e.g. soaps, fatty alcohol sulfates, alkanesulfones), α-olefin sulfonates, fatty alcohol polyglycol ether sulfate; fatty alcohols, ethylene oxide addition products of fatty acids and alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, fatty acids alkanolamides and thickeners, such as methyl- or hydroxy-ethylcellulose, starches, fatty alcohols, paraffin oils, fatty acids, as well as perfume oils and hair protection additives, such as water-soluble cationic polymers, protein rust conductors, pantothene. acid and cholesterin.

The components of the cosmetic carrier are used for producing the hair dye according to the invention in the amounts customary for this purpose.

That is, for example, if the emulsifier is added to all hair dyes, it is 0.5 to 50.
Concentration in weight % and thickener from 0.1 to 2.0 per total hair dye.
Used at a concentration of 5% by weight. The oxidative dye precursor is mixed into the carrier in an amount of 90.2 to 5% by weight, preferably 1 to 3% by weight, based on the total hair dye.

The application of the hair dyes according to the invention can be carried out in weakly acidic, neutral or alkaline media, irrespective of the type of cosmetic preparation, for example creams, gels or shampoos. Application of the hair dye is preferably within the pH range of 8-10.

The application temperature can be in the range 15-40°C. After an action time of about 30 minutes, the hair dye is washed off from the hair to be dyed. The hair is then washed with a mild shampoo and dried. If carriers containing significant surfactants are used, for example color shampoos, post-washing with shampoo is omitted.

The dyeings obtainable with the hair dyes according to the invention have high gloss and excellent heat-two-light-one-wash and rub-fastness properties. The following examples illustrate the subject matter of the invention in detail:
The present invention is not limited to these.

Example t 2-) If syl--chloro-5-aminophenol-hydrochloride 5 g of 4-chloro-2-methyl-5-aminophenol was dissolved in 200 g of ethanol and 0.5 g of Raney nickel.
After the addition of , catalytic hydrogenation is carried out. After the hydrogen atom absorption is completed, the catalyst is partially separated by filtration, and the F solution is acidified with dilute hydrochloric acid. After evaporation to dryness, pale yellow-gray crystals with a melting point of 198° C. (under decomposition) are obtained.

2, 2-Mef-4-chloro-5-ditylaminophenol 4-chloro-2-methyl-5-aminophenol 31
(o, o16Mol), ethyl iodide 2.69 (
0,017Mol'), sodium hydrogen carbonate 1°35
A mixture of 9 (0,016 Mo1) and 50 ml of ethanol' is heated to boiling temperature under reflux cooling for 7 hours. Cooling and water 50rn1. After dilution with water, neutralization with sodium bicarbonate solution and extraction of the solution three times with 50 ml each of acetic acid ethyl ester. The extracts are dried over sodium sulfate and evaporated to dryness. The residue is recrystallized from doluol. Yellow-gray crystals with a melting point of 205° C. are obtained.

12-Methyl-4-chloro-5-(2-hydroxyethyl)aminephenol (a) [β-chloroethyl-(2'chloro-4'methyl-5'hydroxy)-phenyl]-carbamate 2-methyl-4- 9.79 (0.05 Mol) of chloro-5-aminophenol-hydrochloride are suspended in 25 mg of dioxane.

Calcium carbonate 5.5,! i' (0,055Mo1
) and increase the temperature to +90°C. Then, under stirring, chloroformic acid-2-chloroethyl ester 7.99 (0,
055Mo/) was added dropwise and stirred at 90°C for 1 hour. The mixture is then cooled to +20° C. and the mineral salts are separated off by filtration. 100 ml of water are added to the filtered solution and the precipitate formed is separated by filtration.

Yellow-gray crystals with a melting point of 124° C. are obtained.

(blN-((2'-chloro-4'methyl-5'hydroxy)-phenyl)-1,3-oxazolin-2-one 3(a) with 4.3 mol of substance 1o, 69 (0,04Mo1) Add to the caustic soda solution 24-1 at 45°C. After stirring for 20 minutes, add ice water to the reaction mixture. Neutralize with dilute hydrochloric acid. The desired product precipitates out, is separated by filtration and dried at 70°C. Melting point: 198℃~200℃
Yellow-gray crystals are obtained.

(C) Substance 7.3 due to 2-methyl-4-chloro-5-(2-hydroxyethyl)aminephenol 3('b),! i+ (0,032
Mo1) is separated into 20 ml of 5 molar sodium hydroxide solution at 70°C. After 30 minutes of reaction, the solution is cooled to 0° C. and neutralized with concentrated acetic acid. The precipitated product was separated by filtration and 7
Dry at 0°C.

Brown crystals are obtained with a melting point of 111° C. (under decomposition).

For the test of the new coupling component according to the test example 1-3 on the usage technology,
It is used in the form of a hair dye-cream emulsion with the following composition: fatty alcohol Cl2-18 10
．． jil fat fat alcohol, 4+2FJO-sulfate.

(Na-Salt 28%) 25g Water 60f
l Color developer substance 0.0075 mol Coupling substance Inhibitor (N a
tSOs) 1-09 concentrated ammonia solution -=9.5 boiled water
A total of 100 g of the ingredients are mixed one after the other. After the addition of the color developer and the coupling substance, the pH of the emulsion was first adjusted to 9.5 tC using concentrated ammonia solution, and then 100 g of water was added.
to meet.

The oxidative coupling is carried out with hydrogen peroxide solution in 3 as the oxidizing agent. Then, 5 g of hydrogen peroxide solution (3%) is added to Emulsion 10I and mixed.

The dyeing cream is applied in the form of tresses approximately 5 Car long to standard 90% gray hair, without any special pretreatment, and left there for 30 minutes at 35°C.

After the first stage of the dyeing process, the hair is washed with a conventional hair wash and then dried.

The following compound is used as a color developer.

El: p-phenylenediamine! :2:p-) 3:2-chloro-p-phenylenediamine E4:
2.5-diaminoanisole Fi5: N-benzyl-
6:N-(2-hydroxypropyl)-p-7 to p-phenylenediamine 7:N-(p-aminoanisole)-r,y-bis(
2-hydroxyethyl) -1,3-diaminopropane 8: N,N-dimethyv-p-7 unilenediamine K 9: N,N-bis-(2-hydroxyethyl)
-p-phenylenediamine to 10:2,5-diaminobenzyl alcoholff11
1:N-methyl-p-phenylenediamine to 12:N-
(2-Hydroxyethyl)-p-phenylenediamine 15: N-(2-methoxyethyl)-p-7 22-diamine 14: N-butyl-N-sulfobutyl-1)-phenylenediamine K 15: N , N-diethyl-p-phenylenediamine to 16:N-ethyl-N-(2-hydroxyethyl)-
17 to p-phenylenediamine: 2,5-diaminopyridine E18: p-aminophenol E19: 2. '4,5,6-titraaminopyrimidine to 20:2-dimethylamine-4,5,6-driami, nopyrimidine The following compound is used as a coupling substance according to the invention: to 1:2-methyl-4 -chloro-5-aminophenol-hydrochloride 2:2-methyl-4-chloro-5-ditylaminophenol 3:2-methyl-4-chloro-5-(2-hydroxyethyl)-dimininophenol The hair dyeing results are listed in Table 1.

The ninth comparative test for testing the light fastness properties of hair dyes includes the following:
2KV4: 2-chloro-6-methyl-3-7minophenol KV5: 2-methyl-6-chloro-3-aminophenol using the coupling substances known from German Patent No. 3016008 Testing of fastness The light fastness of dyed hair strands was tested using D-TechN 54004 (A
The eight types of blue staining of the light fastness scale, measured according to Chapter 7.5.2
and xenon arc light having a light temperature of 5500-6500'. In addition, the hair bundle and the fiber material specimen were fixed simultaneously on cardboard, and the edges of the specimen were placed parallel to the vertical edge of the specimen support with the edges exposed to [5° sunlight fastness scale type 3 and not exposed to light]. The frame is removed and exposed to light under customary controls until there is an appreciable difference in color between the parts. It is then determined whether the specimen exhibits a change and this is evaluated in comparison to changes in types 1, 2 and 5 of the light fastness scale. It is then further exposed to light until there is an appreciable difference in color between the exposed and unexposed areas of Type 4 light. Replace the cover plate with a larger one. This covers approximately 1/3 of the previously exposed surface parallel to the length. Scale type 6 is exposed to light until the above perceptible color difference occurs. Measurements of lightfastness are made by comparing the contrast on the hair strands with the contrast on the type staining of the lightfastness scale.

The results of this light fastness test are listed in Table ■: Table I Table ■

Claims (7)

[Claims] (1) General formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is a hydrogen atom, an alkyl group having 1-4 carbon atoms, or a hydroxyalkyl group having 2-4 carbon atoms.) -Aminophenol and its water-soluble salts. (2) The m-aminophenol according to claim 1, wherein R is a hydrogen atom. (3) Catalytically hydrogenating 4-chloro-2-methyl-5-nitrophenol to produce 4-chloro-2-methyl-5-aminophenol, and optionally introducing a group R into the amino group by a known method. General formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 2 to 4 carbon atoms.) A method for producing m-aminophenol and its water-soluble salt. (4) General formula I ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R is a hydrogen atom, an alkyl group having 1-4 carbon atoms, or a hydroxyalkyl group having 2-4 carbon atoms.) - The use of aminophenols and their water-soluble salts as coupling substances in oxidative hair dyes together with common color developing substances. (5) As a color developer, p-phenylenediamine, p-tolylenediamine, p-aminophenol or 2,4,
The method of use according to claim 4, which uses 5,6-tetraaminopyridine. (6) General formula I as an oxidation dye precursor ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a hydrogen atom, an alkyl group having 1-4 carbon atoms, or a hydroxyalkyl group having 2-4 carbon atoms. ) 0.0% of the coupling substance per 100g of hair dye.
Hair dye containing an oxidative dye precursor in the form of a cosmetic carrier, characterized in that it contains an amount of 5-10 mMol and a customary color developer. (7) Additionally contains other known coupling substances, and the color developer substance and the coupling substance are mixed in a molar ratio of 1:0.
．． 7. The hair dye according to claim 6, wherein the content of the oxidative dye precursor is 0.2-5.0% by weight of the hair dye.